CA1049952A - Production of electrolytic battery active manganese dioxide - Google Patents
Production of electrolytic battery active manganese dioxideInfo
- Publication number
- CA1049952A CA1049952A CA215,891A CA215891A CA1049952A CA 1049952 A CA1049952 A CA 1049952A CA 215891 A CA215891 A CA 215891A CA 1049952 A CA1049952 A CA 1049952A
- Authority
- CA
- Canada
- Prior art keywords
- ore
- manganese dioxide
- catholyte
- mno2
- anodes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/21—Manganese oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Abstract of the Disclosure This process concerns the direct electro-conversion of low grade manganese ores to high purity manganese dioxide product, which, among other applications, is ideally suited for use in dry cells. The process operating conditions are controlled such that impurities in the ore are substantially eliminated from the product. A decrease in impurity levels in excess of 100 fold can be achieved between the product and the ore feed.
Description
- 104~95;~
Product ~pplications The majox application of the manganese dioxide product is in its use as ~he cathode depolariser in the convent-ional Leclanche dry cell battery. This high grade ~ ~MnO2 is ideally suited for dry cell applications because of its high electrochemical activity. Finely divided synthetic dioxide is also used in ferrite manufacture and for pigments. Other appli-cations are in ceramics, welding rods and the general chemical industry.
The Conventional Process The conventional process for the production of ~ -~n2 from a manganese dioxide feed ore consists of the following steps:-1) High temperature reduction roasting of the natural MnO2 to MnO.
Product ~pplications The majox application of the manganese dioxide product is in its use as ~he cathode depolariser in the convent-ional Leclanche dry cell battery. This high grade ~ ~MnO2 is ideally suited for dry cell applications because of its high electrochemical activity. Finely divided synthetic dioxide is also used in ferrite manufacture and for pigments. Other appli-cations are in ceramics, welding rods and the general chemical industry.
The Conventional Process The conventional process for the production of ~ -~n2 from a manganese dioxide feed ore consists of the following steps:-1) High temperature reduction roasting of the natural MnO2 to MnO.
2~ Acid dissolution of this MnO in the spent electrolyte.
3) Purification of ~he pregnant leach liquoxs (a) with a base, to remove iron, and (b) with a sulphide, to remove heavy metal impurities.
4) Electrolysis of the filtered electrolyte to produce a high purity MnO2 product at the anode according to equation (2) and hydrogen at the cathode:-- 2H~ ~ 2e -~ H2 Notable disadvantages of the conventional process are: a) the need for pretreatment (reduction roasting) of the feed ore which is an energy consuming step with polluting side effects;
b) the evolution of hydrogen from the hot (80-100&) electrolytic cells causes appreciable heat losses due to the greatly increased evaporation of water and can also produce an acid mist which yields an unpleasant working environment and building corrosion;
c) depletion of the solution Mn2~ content.
The Movel Process In essence, the process herein described concerns .. . . .
iO4~9SZ
the electrorefining of manganese dioxide to produce a high grade synthetic product from natural ore. The principal equations 3 describing the cathode and anode reactions are:
Cathode MnO2 + 4H + 2e ~ Mn + 2H2O (1) j Anode Mn + 2H20-~ MnO2+ 4H + 2e (2~
As these equations balance each other in consumption and formation of species, only make-up quantities of other materials are required. This novel process has simultaneously overcome all the disadvantages of the conventional process and has markedly reduced the extent of purification required due to the selectivity of the leach. A further advantage of this novel `! process is a reduction in the cell operating voltage through the r~ high anolyte Mn2 concentrations and thelower cathode potential ~, of the dissolution reaction compared with that for H2 evolution, ~, this giving a notable reduction in power consumption.
;3 As this process is based upon two reversible equations, the nature of the anodic species is only significant to the extent at which alternate reactions may occur at the electrodes.
Thus, it must be noted that while sulphate, chloride and nitrate solutions may be used, sulphate solutions are preferred as these present least operating difficulties.
This invention may be conducted in a cell containing three essential elements -1) a cathode compartment which contains a slurry of particulate MnO2, the Mn content of which is being selectively leached by a reducing environment attributable to the cathode;
2) an anode compartment comprising a manganese containing electrolyte (either the sulphate, chloride or nitrate) from which an MnO2 product is being produced;
` 30 3) an ion-permeable diaphragm, which is impermeable to the part-¦ iculate MnO2 slurry, separating the anode and cathode regions.
~ The present invention will be further illustrated by '~ ' ~ ~ - 2 -. , .
way of the accompanying drawings in which:
. Fig. 1 is a diagrammatic side elevation of an electro-¦ lytic cell configuration for use in the process according to an embodiment of the present invention, Fig. 2 is a flow sheet of a batch or semi batch oper-ation of the process according to a further embodiment of the present invention, and Fig. 3 is a flow sheet of a continuous operation of the process according to another embodiment of the present invention.
~3 A typical such cell is illustrated in Figure 1, this figure being provided to facilitate understanding of the .~
..~
~ 20 , I
:
.; .
' 30 ."~ .
. - 2a -:;
104'39S'~
process and is not to be consi~ered in any way limiting this invention.
The conditions in the anolyte compartment may be controlled to produce a variety of MnO2 products. For example, at 90-98 C, a dense anode deposit of ~-MnO2 may be deposited, whilst at 15-25C, a particulate product may be formed. Typical materials suitable for use at the anode include carbon, lead and titanium, all of which are currently used within the industry.
The temperature conditions in the catholyte are by necessity similar to those selected for the anodic product formation step.
However, markedly different solution conditions may be attained by control of the diaphragm material and electrolysis conditions.
Correct selection of the diaphragm material is essential for the control of anolyte/catholyte acidities as the anode reaction is acid producing and Mn + ion consuming, whilst the cathode reaction is acid consuming and Mn2~ ion producing.
The conditions under which this invention operates are:
i) Anode Com~artment A temperature from about 15C to the solution boiling point (about 120&), with a preferred temperature range of 80-100C for the production of an adherent anode deposit of ~ -MnO2, and of 15-25C for a particulate pro-duct; a solution manganese content of about 20 g/l Mn to about 200 g/l Mn, with a preferred value of 80 to 130 g/l, as this ensures a high deposit efficiency ~ 95%; an operating solution acidity of up to about SN, with a preferred acidity of about 2~;
and an anode curren~ density of about 30 to about 250 Amp/m for an adherent high temperature deposit and of about 1000 to 4000 Amp/m for a particulate deposit. Whilst from a capital invest-~ 30 ment standpoint, high current densities are desirable, product properties, current efficiencies and cell operating conditions are superior at intermediate current densities, thus the preferred current density range is 30 to 120 A/m2 for titanium anodes and -~ o~sz ~o t~ 140 ~/m2 for c~rbon anodes to obtain a conventional ad-herent deposit. As those skilled in the art are well aware, the high pre~erred manganese concentrations facilitate operation at high current densities.
~i) Cathode compartment The cathode solution conditions are related to those in the anolyte by the relative rates of electrolytic generation or consumption and diffusion through the p diaphragm. The ~ff~a~d colution temperatures are as given for q ~ .
the anode, namely 15 C to the solution boiling point; ns~L~
dissolved manganese contents are from 30 g/l to about 220 g/l Mn; ~n~EF~ i solution acidities are from about pH7 to pH0 with a value of about pH4 to pH0.5 preferred. In fact low catholyte acidities are particularly important in avoiding the dissolution of non-manganese elements.
A solids loading of about 20 to 350 g/l may be used whilst the preferred range is about 50 to 200 g/l. The ore ~eed should preferably be finely ground, say ~ 95% less than 50~ m, to attain high dissolution efficiency, but the process is opcrable with larger particle sizes. Together with catholyte acidity, selection of the cathode material and current density are particularly important to control the selective leaching of MnO2 and to prevent the dissolution of impurities. Typical cathode current densities of 5 to 400 Amp/m2 may be used with preferred current densities of 25 to 100 Amp/m2.
' ExamPle ~he following example is provided to illustrate this invention but should not be construed as limiting this in-.. . . . .
vention in any way whatsoever.
1200g of MnO2 ore was agitated in 81 of MnS04 solution (105 g/l Mn + and 2.9 g/l H2S04) in a diaphragm cell containing three titanium anodes, each 12 cm x 10 cm submerged - area and enclosed in polypropylene cloth diaphragm bags, and four graphite cathodes, each 12 cm x 10 cm submerged area, external to 10~995'~
the diaphragm bags.
Current was passed at 60A/m2 of anode area for 96 hours at a temperature of 90C. The average cell voltage was 2.1 Volt. The power consumption was 1.24 ~H/I~g.
The adherent MnO2 produc~ was stripped from ths titanium anodes and the catholyte slurry filtered to recover the residue.
In Table 1 below, it can be seen that product of high purity is formed and a large reduction in impurity level, one hundred fold in the case of Fe, can be obtained between feed ore and product.
TABLE 1: ANALYTICAL RESULTS
Component Ore Product Residue Electrolyte Start Finish H2S4 ~ ~2 . 9g/1 Anolyte Catho-lyte 98. Og/l 9.8g/1 Nn 45% 62% 20% 9 .5% 9 . 3%
Fe 20,000ppm200ppm 35,000ppml90mg/1 320mg/1 Cu 150 20 250 8 6 Pb 100 50 200 14 14 Zn 70 20 100 78 70 lii 100 20 200. 130 110 Co 70 30 100 114 100 Cr 60 10 100 2 4 Mo 440~ - 1,000 Ca 16,000 200 30,000 100 400 Mg 10 ~ 000 - 25 ~ 000 240 600 K 5~500 200 12~000 40 120 ~a 1,040 20 2,300 40 200 ~um~er of qrams 1,200 675_ 560 .
.' :
10~9'~5~
In Table 2, it can be seen that product o~ high ~lectroch~mical activity can be prepared. The product prepared has been compared with a standard electrolytic manganese dioxide from Japan. The m~thod used to d~termine the electrochemical activity was by the Iiornfeil test. MLanganese dioxide sample (0.50g) and acetylene black (0.20g~ are mixed as a slurry wi~h electrolyte solution (I~ornfeil 2 solution) to a standard moisture level. This mix is then added into the Kornfeil cell and the wet black mix compressed with the carbon catho~e rod by loadin~ with a 2 kg weight. The resulting Kornfeil pellet was maintained under this load and discharged between the carbon and zinc electrodes at constant current drains. The residual cell voltacJe ~as determined as a function of time by a pulse-interrupt technicue, to a final voltage of 1.00 volt. The time of discharye is ta.sQn as a measure of the electrochemical activity of the manganese dioxide.
TABIJ3 2: EIIECTROOEIEMICAI- ACT IVIT~r OE' PRODUCT
Product Time to l.OV at high Time to l.OV at low current drain of 60m~ current drain o 12 mA
20 Standard Electrolytic 4,000 sec. 25,200 sec;
~n2 (Japan) Exam~le Product 4,300 27,000 l~hilst this invention concerns a process for the electrorefining of MnO2, it must be noted that a variety or process flow sheets are possible, the following illustrations of which are provided but in no way should be considered limiting.
The following discussion has been limited to the formation of a high temperature (80-100C) adherent ~ -MnO2 pro-duct fox illustrative purposes only.
The simplest process flow sheet (Figure 2) is the addition of ground ore to an electrolytic cell containing a pre-pared electrolyte, and the batchwise or semi-batchwise dissolution ,.. . ~.
.
10~9S'~
of ore occurs. ~en thc electrolysis is ceased because of ore depletion or sludge accumulation, the manganese deficient residue is separated from the solution and the solution is returned to the cell and the process repeated. The anode may be removed periodically and the adherent deposit stripped at any time throughout the batch dissolution. Modifications of the above, including continuous ore addition to a non-flow cell or a con- -tinuous flow systcm via a multiple series of cells, are obvious to those skilled in the art.
A refinement of the above single cell is the con-tinuous removal of a portion of the catholyte, and the return of the solution, after filtration, to the cell, for example to the anolyte (Figure 3). If desired, some form or purification treatment, e.g. pH adjustment, may be carried out before return-ing th- electrolyte to the cell.
..
b) the evolution of hydrogen from the hot (80-100&) electrolytic cells causes appreciable heat losses due to the greatly increased evaporation of water and can also produce an acid mist which yields an unpleasant working environment and building corrosion;
c) depletion of the solution Mn2~ content.
The Movel Process In essence, the process herein described concerns .. . . .
iO4~9SZ
the electrorefining of manganese dioxide to produce a high grade synthetic product from natural ore. The principal equations 3 describing the cathode and anode reactions are:
Cathode MnO2 + 4H + 2e ~ Mn + 2H2O (1) j Anode Mn + 2H20-~ MnO2+ 4H + 2e (2~
As these equations balance each other in consumption and formation of species, only make-up quantities of other materials are required. This novel process has simultaneously overcome all the disadvantages of the conventional process and has markedly reduced the extent of purification required due to the selectivity of the leach. A further advantage of this novel `! process is a reduction in the cell operating voltage through the r~ high anolyte Mn2 concentrations and thelower cathode potential ~, of the dissolution reaction compared with that for H2 evolution, ~, this giving a notable reduction in power consumption.
;3 As this process is based upon two reversible equations, the nature of the anodic species is only significant to the extent at which alternate reactions may occur at the electrodes.
Thus, it must be noted that while sulphate, chloride and nitrate solutions may be used, sulphate solutions are preferred as these present least operating difficulties.
This invention may be conducted in a cell containing three essential elements -1) a cathode compartment which contains a slurry of particulate MnO2, the Mn content of which is being selectively leached by a reducing environment attributable to the cathode;
2) an anode compartment comprising a manganese containing electrolyte (either the sulphate, chloride or nitrate) from which an MnO2 product is being produced;
` 30 3) an ion-permeable diaphragm, which is impermeable to the part-¦ iculate MnO2 slurry, separating the anode and cathode regions.
~ The present invention will be further illustrated by '~ ' ~ ~ - 2 -. , .
way of the accompanying drawings in which:
. Fig. 1 is a diagrammatic side elevation of an electro-¦ lytic cell configuration for use in the process according to an embodiment of the present invention, Fig. 2 is a flow sheet of a batch or semi batch oper-ation of the process according to a further embodiment of the present invention, and Fig. 3 is a flow sheet of a continuous operation of the process according to another embodiment of the present invention.
~3 A typical such cell is illustrated in Figure 1, this figure being provided to facilitate understanding of the .~
..~
~ 20 , I
:
.; .
' 30 ."~ .
. - 2a -:;
104'39S'~
process and is not to be consi~ered in any way limiting this invention.
The conditions in the anolyte compartment may be controlled to produce a variety of MnO2 products. For example, at 90-98 C, a dense anode deposit of ~-MnO2 may be deposited, whilst at 15-25C, a particulate product may be formed. Typical materials suitable for use at the anode include carbon, lead and titanium, all of which are currently used within the industry.
The temperature conditions in the catholyte are by necessity similar to those selected for the anodic product formation step.
However, markedly different solution conditions may be attained by control of the diaphragm material and electrolysis conditions.
Correct selection of the diaphragm material is essential for the control of anolyte/catholyte acidities as the anode reaction is acid producing and Mn + ion consuming, whilst the cathode reaction is acid consuming and Mn2~ ion producing.
The conditions under which this invention operates are:
i) Anode Com~artment A temperature from about 15C to the solution boiling point (about 120&), with a preferred temperature range of 80-100C for the production of an adherent anode deposit of ~ -MnO2, and of 15-25C for a particulate pro-duct; a solution manganese content of about 20 g/l Mn to about 200 g/l Mn, with a preferred value of 80 to 130 g/l, as this ensures a high deposit efficiency ~ 95%; an operating solution acidity of up to about SN, with a preferred acidity of about 2~;
and an anode curren~ density of about 30 to about 250 Amp/m for an adherent high temperature deposit and of about 1000 to 4000 Amp/m for a particulate deposit. Whilst from a capital invest-~ 30 ment standpoint, high current densities are desirable, product properties, current efficiencies and cell operating conditions are superior at intermediate current densities, thus the preferred current density range is 30 to 120 A/m2 for titanium anodes and -~ o~sz ~o t~ 140 ~/m2 for c~rbon anodes to obtain a conventional ad-herent deposit. As those skilled in the art are well aware, the high pre~erred manganese concentrations facilitate operation at high current densities.
~i) Cathode compartment The cathode solution conditions are related to those in the anolyte by the relative rates of electrolytic generation or consumption and diffusion through the p diaphragm. The ~ff~a~d colution temperatures are as given for q ~ .
the anode, namely 15 C to the solution boiling point; ns~L~
dissolved manganese contents are from 30 g/l to about 220 g/l Mn; ~n~EF~ i solution acidities are from about pH7 to pH0 with a value of about pH4 to pH0.5 preferred. In fact low catholyte acidities are particularly important in avoiding the dissolution of non-manganese elements.
A solids loading of about 20 to 350 g/l may be used whilst the preferred range is about 50 to 200 g/l. The ore ~eed should preferably be finely ground, say ~ 95% less than 50~ m, to attain high dissolution efficiency, but the process is opcrable with larger particle sizes. Together with catholyte acidity, selection of the cathode material and current density are particularly important to control the selective leaching of MnO2 and to prevent the dissolution of impurities. Typical cathode current densities of 5 to 400 Amp/m2 may be used with preferred current densities of 25 to 100 Amp/m2.
' ExamPle ~he following example is provided to illustrate this invention but should not be construed as limiting this in-.. . . . .
vention in any way whatsoever.
1200g of MnO2 ore was agitated in 81 of MnS04 solution (105 g/l Mn + and 2.9 g/l H2S04) in a diaphragm cell containing three titanium anodes, each 12 cm x 10 cm submerged - area and enclosed in polypropylene cloth diaphragm bags, and four graphite cathodes, each 12 cm x 10 cm submerged area, external to 10~995'~
the diaphragm bags.
Current was passed at 60A/m2 of anode area for 96 hours at a temperature of 90C. The average cell voltage was 2.1 Volt. The power consumption was 1.24 ~H/I~g.
The adherent MnO2 produc~ was stripped from ths titanium anodes and the catholyte slurry filtered to recover the residue.
In Table 1 below, it can be seen that product of high purity is formed and a large reduction in impurity level, one hundred fold in the case of Fe, can be obtained between feed ore and product.
TABLE 1: ANALYTICAL RESULTS
Component Ore Product Residue Electrolyte Start Finish H2S4 ~ ~2 . 9g/1 Anolyte Catho-lyte 98. Og/l 9.8g/1 Nn 45% 62% 20% 9 .5% 9 . 3%
Fe 20,000ppm200ppm 35,000ppml90mg/1 320mg/1 Cu 150 20 250 8 6 Pb 100 50 200 14 14 Zn 70 20 100 78 70 lii 100 20 200. 130 110 Co 70 30 100 114 100 Cr 60 10 100 2 4 Mo 440~ - 1,000 Ca 16,000 200 30,000 100 400 Mg 10 ~ 000 - 25 ~ 000 240 600 K 5~500 200 12~000 40 120 ~a 1,040 20 2,300 40 200 ~um~er of qrams 1,200 675_ 560 .
.' :
10~9'~5~
In Table 2, it can be seen that product o~ high ~lectroch~mical activity can be prepared. The product prepared has been compared with a standard electrolytic manganese dioxide from Japan. The m~thod used to d~termine the electrochemical activity was by the Iiornfeil test. MLanganese dioxide sample (0.50g) and acetylene black (0.20g~ are mixed as a slurry wi~h electrolyte solution (I~ornfeil 2 solution) to a standard moisture level. This mix is then added into the Kornfeil cell and the wet black mix compressed with the carbon catho~e rod by loadin~ with a 2 kg weight. The resulting Kornfeil pellet was maintained under this load and discharged between the carbon and zinc electrodes at constant current drains. The residual cell voltacJe ~as determined as a function of time by a pulse-interrupt technicue, to a final voltage of 1.00 volt. The time of discharye is ta.sQn as a measure of the electrochemical activity of the manganese dioxide.
TABIJ3 2: EIIECTROOEIEMICAI- ACT IVIT~r OE' PRODUCT
Product Time to l.OV at high Time to l.OV at low current drain of 60m~ current drain o 12 mA
20 Standard Electrolytic 4,000 sec. 25,200 sec;
~n2 (Japan) Exam~le Product 4,300 27,000 l~hilst this invention concerns a process for the electrorefining of MnO2, it must be noted that a variety or process flow sheets are possible, the following illustrations of which are provided but in no way should be considered limiting.
The following discussion has been limited to the formation of a high temperature (80-100C) adherent ~ -MnO2 pro-duct fox illustrative purposes only.
The simplest process flow sheet (Figure 2) is the addition of ground ore to an electrolytic cell containing a pre-pared electrolyte, and the batchwise or semi-batchwise dissolution ,.. . ~.
.
10~9S'~
of ore occurs. ~en thc electrolysis is ceased because of ore depletion or sludge accumulation, the manganese deficient residue is separated from the solution and the solution is returned to the cell and the process repeated. The anode may be removed periodically and the adherent deposit stripped at any time throughout the batch dissolution. Modifications of the above, including continuous ore addition to a non-flow cell or a con- -tinuous flow systcm via a multiple series of cells, are obvious to those skilled in the art.
A refinement of the above single cell is the con-tinuous removal of a portion of the catholyte, and the return of the solution, after filtration, to the cell, for example to the anolyte (Figure 3). If desired, some form or purification treatment, e.g. pH adjustment, may be carried out before return-ing th- electrolyte to the cell.
..
Claims (10)
1. A process for the production of high grade ?MnO2 from manganese dioxide ore in an electrochemical cell having one or more inert anodes, immersed in an aqueous anolyte having a solution manganese content of 20 g/l Mn to 200 g/l Mn and an acidity of up to 5N, and one or more inert cathodes, immersed in a slurry consisting of particulate manganese dioxide ore and an aqueous catholyte having a solution manganese content of 30 g/l Mn to 220 g/l Mn and a pH below 7, the anodes and cathodes disposed on opposite sides of one or more porous diaphragms, the process consisting of applying a direct current potential between the anodes and cathodes to reduce manganese dioxide slurry to ionic manganese which diffuses through the diaphragms and is oxidised at the anodes where ?MnO2 is formed, the anode current density being 20 to 250 Amp/m2 at a cell temperature of from 15 to 25°C or 1,000 to 4,000 Amp/m2 at a cell temperature of 80 to 100°C
and the cathode current density being 5 to 400 Amps/m2.
and the cathode current density being 5 to 400 Amps/m2.
2. A process as in claim 1 in which the electrolyte comprises the anion group, sulphate.
3. A process as claimed in claim 1 in which the electrolyte comprises the anion group, chloride.
4. A process as claimed in claim 1 in which the electrolyte comprises the anion group, nitrate.
5. A process as claimed in claim 1 in which the anode current density is from about 30 to 140 Amp/m2.
6. A process as claimed in claim 1 in which the anolyte contains about 80 to 130 g/l Mn and about 2N acid.
7. A process as claimed in claim 1 in which the cathode current density is 25 to 100 Amp/m2.
8. A process as claimed in claim 1 in which the ore content of the catholyte is about 20 to 350 g/l.
9. A process as claimed in claim 1 in which the ore content of the catholyte is about 50 to 200 g/l.
10. A process as claimed in claim 1, in which the acid content in the catholyte is such that the pH is in the range of about pH4 to pH0,5.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AUPB607173 | 1973-12-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1049952A true CA1049952A (en) | 1979-03-06 |
Family
ID=3765836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA215,891A Expired CA1049952A (en) | 1973-12-20 | 1974-12-12 | Production of electrolytic battery active manganese dioxide |
Country Status (7)
| Country | Link |
|---|---|
| BE (1) | BE823566A (en) |
| BR (1) | BR7410726D0 (en) |
| CA (1) | CA1049952A (en) |
| DE (1) | DE2460604A1 (en) |
| FR (1) | FR2255261A1 (en) |
| IT (1) | IT1024434B (en) |
| ZA (1) | ZA747811B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2553568B1 (en) * | 1983-10-14 | 1986-04-11 | Gipelec | ELECTROCHEMICAL GENERATOR WITH NONAQUEOUS ELECTROLYTE, WHOSE POSITIVE ELECTRODE IS BASED ON MANGANESE BIOXIDE |
-
1974
- 1974-12-09 ZA ZA00747811A patent/ZA747811B/en unknown
- 1974-12-12 IT IT54518/74A patent/IT1024434B/en active
- 1974-12-12 CA CA215,891A patent/CA1049952A/en not_active Expired
- 1974-12-19 BE BE151688A patent/BE823566A/en unknown
- 1974-12-19 FR FR7442058A patent/FR2255261A1/en active Granted
- 1974-12-20 BR BR10726/74A patent/BR7410726D0/en unknown
- 1974-12-20 DE DE19742460604 patent/DE2460604A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| FR2255261B1 (en) | 1981-05-29 |
| FR2255261A1 (en) | 1975-07-18 |
| IT1024434B (en) | 1978-06-20 |
| ZA747811B (en) | 1976-01-28 |
| BE823566A (en) | 1975-04-16 |
| DE2460604A1 (en) | 1975-07-03 |
| BR7410726D0 (en) | 1975-09-02 |
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